WO2004011509A1 - Polymeres fluores, resines photosensibles et procedes de microlithographie - Google Patents

Polymeres fluores, resines photosensibles et procedes de microlithographie Download PDF

Info

Publication number
WO2004011509A1
WO2004011509A1 PCT/US2003/022912 US0322912W WO2004011509A1 WO 2004011509 A1 WO2004011509 A1 WO 2004011509A1 US 0322912 W US0322912 W US 0322912W WO 2004011509 A1 WO2004011509 A1 WO 2004011509A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
fluorine
containing copolymer
repeat unit
unit derived
Prior art date
Application number
PCT/US2003/022912
Other languages
English (en)
Inventor
Andrew Edward Feiring
Frank Leonard Schadt, Iii
Toshiyuki Ogata
Koutaro Endo
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to AU2003254112A priority Critical patent/AU2003254112A1/en
Priority to EP03771715A priority patent/EP1551887A4/fr
Priority to JP2004524696A priority patent/JP4303202B2/ja
Priority to US10/521,412 priority patent/US20050203262A1/en
Priority to CA002493926A priority patent/CA2493926A1/fr
Publication of WO2004011509A1 publication Critical patent/WO2004011509A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the present invention pertains to copolymers useful for photoimaging compositions and, in particular, photoresist compositions (positive-working and/or negative-working) for imaging in the production of semiconductor devices.
  • the polymers of the present invention comprise a repeat unit that contains a fluoroalcohol-derived functional group and a repeat unit derived from an alkyl-substituted hydroxymethylacrylate comonomer or a polycycle-substituted acrylate in which the polycyclic group contains a hydroxy substituent.
  • the polymers are especially useful in photoresist compositions having high UV transparency (particularly at short wavelengths, e.g. ,157 nm) which are useful as base resins in resists and potentially in many other applications. Description of Related Art
  • UV light or other electromagnetic radiation impinges on a material containing a photoactive component to induce a physical or chemical change in that material.
  • a useful or latent image is thereby produced which can be processed into a useful image for semiconductor device fabrication.
  • electromagnetic radiation in the far or extreme ultraviolet (UV) is needed.
  • Photolithography using 193 nm exposure is a leading candidate for future microelectronics fabrication using 0.18 ⁇ m and 0.13 ⁇ m design rules; photolithography using 157 nm exposure may be needed for 0.100 ⁇ m or less design rules.
  • the opacity of traditional near-UV and far- UV organic photoresists at 193 nm or shorter wavelengths precludes their use in single-layer schemes at 157 nm.
  • Photoresists comprising copolymers with fluoroalcohol functional groups have been disclosed in WO 00/67072. Copolymers of fluorinated alcohol monomers with other comonomers have been reported (U.S. 3,444,148 and JP 62186907 A2). These patents are directed to membrane or other non-photosensitive films or fibers, and do not teach the use of fluorinated alcohol comonomers in photosensitive layers (e.g., resists).
  • This invention relates to a fluorine-containing copolymer comprising: (a) a first repeat unit derived from an ethylenically unsaturated compound containing a functional group having the structure:
  • R is H, F, or a C1-C5 alkyl or fluoroalkyl group; R" is a polycyclic C5-C50 alkyl group containing at least one hydroxy group; and
  • R'" is a C-
  • This invention also provides photoresist compositions comprising: (a) a fluorine-containing copolymer comprising:
  • R" is a polycyclic C5-C50 alkyl group containing at least one hydroxy group
  • R'" is a C1-C25 alkyl group; and (b) a photoactive component.
  • This invention also provides a process for preparing a photoresist image on a substrate comprising, in order: (1) applying a coatable photoresist composition on a substrate, wherein the coatable photoresist composition comprises:
  • a fluorine-containing copolymer comprising: (i) a first repeat unit derived from an ethylenically unsaturated compound containing a functional group having the structure:
  • R is H, F, or a C1-C5 alkyl or fluoroalkyl group; R" is a polycyclic C 5 -C 50 alkyl group containing at least one hydroxy group; and
  • R' is a C1-C25 alkyl group
  • This invention also provides an article of manufacture comprising: (a) a substrate; and (b) a photoresist composition comprising:
  • Rf and Rf' are the same or different C
  • R is H, F, or a C1-C5 alkyl or fluoroalkyl group; R" is a polycyclic C5-C50 alkyl group containing at least one hydroxy group; and R'" is a C-j-C 2 5 alkyl group; and (ii) a photoactive component.
  • a fluorine-containing copolymer of this invention comprises a repeat unit derived from at least one ethylenically unsaturated compound containing a functional group derived from a fluoroalcohol or protected fluoroalcohol functional group.
  • This functional group contains fluoroalkyl groups, designated Rf and Rf', which can be partially or fully fluorinated alkyl groups.
  • Rf and Rf are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF 2 ) n wherein n is 2 to 10.
  • the phrase "taken together" indicates that R f and Rf are not separate, discrete fluorinated alkyl groups, but that together they form a ring structure such as is illustrated below in case of a 5-membered ring:
  • Rf and R f ' must be sufficiently fluorinated to impart acidity to the hydroxyl (-OH) of the corresponding fluoroalcohol functional group, such that the hydroxyl proton can be substantially removed in basic media (e.g., aqueous sodium hydroxide or tetraalkylammonium hydroxide solution).
  • basic media e.g., aqueous sodium hydroxide or tetraalkylammonium hydroxide solution.
  • there is sufficient fluorine in the fluoroalcohol functional group such that the hydroxyl group has a pKa value of 5 - 11.
  • Rf and R ' are independently perfluoroalkyl groups of 1 to 5 carbon atoms, most preferably, trifluoromethyl (CF3).
  • the number of fluoroalcohol groups is determined for a given composition by optimizing the amount needed for good development in aqueous alkaline developer.
  • CH 2 CHOCH 2 CH 2 OCH 2 C(CF 3 ) 2 OH
  • CH 2 CHO(CH 2 ) 4 OCH 2 C(CF 3 ) 2 OH
  • the fluorinated alcohol is a fluorinated alcohol substituted norbomene, particularly hexafluoroisopropanol substituted norbomene. NB-F-OH is most preferred.
  • R' can be optionally substituted by one or more halogen, ether oxygen, ester or ketone carbonyl groups.
  • R'" contains 1 to 20 carbon atoms.
  • a preferred alkyl group, R'" is one that is acid-labile. Examples of acid- labile alkyl groups include, but are not limited to, tertiary alkyl groups such as tertiary butyl and 2-methyl-2-adamantyl, and -substituted cyclic ethers such as 2-tetrahydropyranyl and 2-tetrahydrofuranyl.
  • the polycyclic group, R contains from 5 to 50 carbon atoms, preferably 5 to 30 carbon atoms, and at least one hydroxyl substituent and is optionally substituted by one or more halogen, ether oxygen, ester or ketone carbonyl groups.
  • R" can have one or more fluorine substituents.
  • the fluorine-containing copolymer can also comprise a repeat unit derived from an ethylenically unsaturated compound (a fluoroolefin) containing at least one fluorine atom attached to an ethylenically unsaturated carbon.
  • a fluoroolefin ethylenically unsaturated compound
  • This fluoroolefin comprises 2 to 20 carbon atoms.
  • a preferred fluoroolefin is tetrafluoroethylene.
  • the fluorine-containing polymer can also comprise a repeat unit derived from a cyclic or polycyclic unsaturated compound, such as those represented by structures (H) and (I),
  • R 1 to R 8 and R 1 to R 14 are the same or different and each represents a hydrogen atom, a halogen atom, a carboxyl group, a C 3 to C14 secondary or tertiary alkyl carboxylate, a hydrocarbon group or a substituted hydrocarbon group.
  • Representative comonomers having structure H include, but are not limited to: ⁇ j ( nor b om e n e) ,
  • Representative comonomers having structure I include, but are not limited to:
  • Bifunctional compounds that can initially provide crosslinking and subsequently be cleaved (e.g., upon exposure to strong acid) are also useful as comonomers in the copolymers of this invention.
  • Photoresist compositions, incorporating copolymers comprising these bifunctional monomers, can have improved development and imaging characteristics, since exposure to light photochemically generates strong acid or base,
  • the preferred process for polymerizing the fluorine-containing copolymers of this invention is radical addition polymerization, which was found to avoid the problem of the hydroxy-functionalized acrylate interfering with the polymerization catalyst.
  • Any suitable polymerization initiator such as di-(4-tert-butylcyclohexyl)peroxy-dicarbonate, can be used under appropriate conditions.
  • the polymerization pressure can range from about 50 to about 10,000 psig, preferably from about 200 to about 1,000 psig.
  • the polymerization temperature can range from about 30 °C to about 120 °C, preferably from about 40 °C to about 80 °C.
  • Suitable solvents include 1 ,1,2-trichlorofluoroethane and non- chlorofluorocarbon solvents such as 1 ,1 ,1 ,3,3-pentafluorobutane.
  • the polymerization process is further enhanced by a semi-batch synthesis. In the semibatch synthesis, a part of the monomer mixture is placed in the reaction vessel and then, portionwise or continuously, the remaining monomers and initiator are added to the vessel throughout the polymerization process.
  • Each fluorine-containing copolymer of this invention has an absorption coefficient of less than 4.0 ⁇ nrr 1 at 157 nm, preferably less than 3.5 ⁇ m- at 157 nm, more preferably, less than 3.0 ⁇ nr 1 at 157 nm, and, still more preferably, less than 2.5 ⁇ rrr 1 at 157 nm.
  • the fluorine-containing copolymers of the resist compositions of this invention can contain one or more components having protected acidic fluorinated alcohol groups (e.g., -C(R f )(Rf')OR a , where R a is not H) or other acid groups that can yield hydrophilic groups by the reaction with acids or bases generated photolytically from photoactive compounds
  • protected acidic fluorinated alcohol groups e.g., -C(R f )(Rf')OR a , where R a is not H
  • R a is not H
  • a given protected fluorinated alcohol group contains a protecting group that protects the fluorinated alcohol group from exhibiting its acidity while in this protected form.
  • a given protected acid group (R a ) is normally chosen on the basis of its being acid-labile, such that when acid is produced upon imagewise exposure, it will catalyze deprotection of the protected acidic fluorinated alcohol groups and production of hydrophilic acid groups that are necessary for development under aqueous conditions.
  • a protected fluoroalcohol with this particular protecting group can be obtained by reaction of chloromethylmethyl ether with the fluoroalcohol.
  • An especially preferred protected fluoroalcohol group has the structure:
  • Rf and Rf are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF 2 ) n wherein n is 2 to 10; R 15 is H, a linear alkyl group of 1 to 10 carbon atoms, or a branched alkyl group of 3 to 10 carbon atoms.
  • Carbonates formed from a fluorinated alcohol and a tertiary aliphatic alcohol can also be used as protected acidic fluorinated alcohol groups.
  • the fluorine-containing copolymers of this invention can also contain other types of protected acidic groups that yield an acidic group upon exposure to acid.
  • types of protected acidic groups include, but are not limited to: A) esters capable of forming, or rearranging to, a tertiary cation; B) esters of lactones; C) acetal esters; D) ⁇ -cyclic ketone esters; E) ⁇ -cyclic ether esters; and F) esters which are easily hydrolyzable because of anchimeric assistance, such as MEEMA (methoxy ethoxy ethyl methacrylate).
  • MEEMA methoxy ethoxy ethyl methacrylate
  • category A Some specific examples in category A) are t-butyl ester, 2-methyl- 2-adamantyl ester, and isobornyl ester.
  • the components having protected groups are repeat units having protected acid groups that have been incorporated in the base copolymer resins of the compositions (as discussed above).
  • the protected acid groups are present in one or more comonomers that are polymerized to form a given copolymeric base resin of this invention.
  • a copolymeric base resin can be formed by copolymerization with an acid- containing comonomer and then subsequently acid functionality in the resulting acid-containing copolymer can be partially or wholly converted by appropriate means to derivatives having protected acid groups.
  • the copolymers of this invention can be used to make photoresists by combining the copolymers with at least one photoactive component, a compound that affords either acid or base upon exposure to actinic radiation. If an acid is produced upon exposure to actinic radiation, the PAC is termed a photoacid generator (PAG). If a base is produced upon exposure to actinic radiation, the PAC is termed a photobase generator (PBG).
  • PAG photoacid generator
  • PBG photobase generator
  • Suitable photoacid generators are disclosed in WO 00/66575. Suitable photoacid generators for this invention include, but are not limited to, 1) sulfonium salts (structure I), 2) iodonium salts (structure II), and 3) hydroxamic acid esters, such as structure III.
  • R16-R18 are independently substituted or unsubstituted aryl or substituted or unsubstituted C7-C 2Q alkylaryl (aralkyl).
  • Representative aryl groups include, but are not limited to, phenyl and naphthyl.
  • Suitable substituents include, but are not limited to, hydroxyl (-OH) and C r C 20 alkyloxy (e.g., -OC 10 H 21 ).
  • dissolution inhibitors can be added to photoresists derived from the copolymers of this invention.
  • dissolution inhibitors for far and extreme UV resists (e.g., 193 nm resists) should be designed/chosen to satisfy multiple materials needs including dissolution inhibition, plasma etch resistance, and adhesion behavior of resist compositions comprising a given Dl additive.
  • Some dissolution inhibiting compounds also serve as plasticizers in resist compositions.
  • suitable dissolution inhibitors are disclosed in WO 00/66575.
  • the photoresists of this invention can either be positive-working photoresists or negative-working photoresists, depending upon choice of components in the fluoropolymer, presence or absence of optional dissolution inhibitor and crosslinking agents, and the choice of developer (solvent used in development).
  • positive-working photoresists the resist polymer becomes more soluble and/or dispersible in a solvent used in development in the imaged or irradiated areas whereas in a negative- working photoresist, the resist polymer becomes less soluble and/or dispersible in the imaged or irradiated areas.
  • irradiation causes the generation of acid or base by the photoactive component discussed above.
  • the acid or base may catalyze removal of protecting groups from the fluoroalcohol and optionally other acidic groups present in a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group or a protected fluoroalcohol functional group having the structure:
  • Rf and Rf' are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF 2 ) n wherein n is 2 to 10 and R a is hydrogen or a protected functional group.
  • Development in an aqueous base such a tetramethylammonium hydroxide would result in the formation of a positive image whereas development in an organic solvent or critical fluid (having moderate to low polarity), would results in a negative-working system in which exposed areas remain and unexposed areas are removed. Positive-working photoresists are preferred.
  • a variety of different crosslinking agents can be employed as required or optional photoactive component(s) in the negative-working mode of this invention.
  • crosslinking agent is required in embodiments that involve insolubilization in developer solution as a result of crosslinking, but is optional in preferred embodiments that involve insolubilization in developer solution as a result of polar groups being formed in exposed areas that are insoluble in organic solvents and critical fluids having moderate/low polarity).
  • Suitable crosslinking agents include, but are not limited to, various bis-azides, such as 4,4'-diazidodiphenyl sulfide and 3,3'-diazidodiphenyl sulfone.
  • the reactive species e.g., nitrenes
  • Photoresists of this invention can contain additional optional components.
  • optional components include, but are not limited to, resolution enhancers, adhesion promoters, residue reducers, coating aids, plasticizers, and T g (glass transition temperature) modifiers.
  • the photoresist compositions of this invention are sensitive in the ultraviolet region of the electromagnetic spectrum and especially to those wavelengths ⁇ 365 nm.
  • Imagewise exposure of the resist compositions of this invention can be done at many different UV wavelengths including, but not limited to, 365 nm, 248 nm, 193 nm, 157 nm, and lower wavelengths.
  • Imagewise exposure is preferably done with ultraviolet light of 248 nm, 193 nm, 157 nm, or lower wavelengths, preferably it is done with ultraviolet light of 193 nm, 157 nm, or lower wavelengths, and most preferably, it is done with ultraviolet light of 157 nm or lower wavelengths.
  • Imagewise exposure can either be done digitally with a laser or equivalent device or non-digitally with use of a photomask.
  • Digital imaging with a laser is preferred.
  • Suitable laser devices for digital imaging of the compositions of this invention include, but are not limited to, an argon- fluorine excimer laser with UV output at 193 nm, a krypton-fluorine excimer laser with UV output at 248 nm, and a fluorine (F2) laser with output at 157 nm.
  • UV light of lower wavelength for imagewise exposure corresponds to higher resolution (lower resolution limit)
  • the use of a lower wavelength e.g., 193 nm or 157 m or lower
  • a higher wavelength e.g., 248 nm or higher
  • the fluorine-containing copolymers in the resist compositions of this invention must contain sufficient functionality for development following imagewise exposure to UV light.
  • the functionality is acid or protected acid such that aqueous development is possible using a basic developer such as sodium hydroxide solution, potassium hydroxide solution, or ammonium hydroxide solution.
  • Some preferred fluorine- containing copolymers in the resist compositions of this invention are acid- containing copolymers or homopolymers comprised of at least one fluoroalcohol-containing monomer of structural unit:
  • Rf and R are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF 2 ) n wherein n is 2 to 10.
  • the level of acidic fluoroalcohol groups is determined for a given composition by optimizing the amount needed for good development in aqueous alkaline developer.
  • the photoresist composition may require that the binder material contain sufficient acid groups (e.g., fluoroalcohol groups) and/or protected acid groups that are at least partially deprotected upon exposure to render the photoresist (or other photoimageable coating composition) processable in aqueous alkaline developer.
  • the photoresist layer will be removed during development in portions which have been exposed to UV radiation but will be substantially unaffected in unexposed portions.
  • aqueous alkaline systems such as aqueous solutions containing 0.262 N tetramethylammonium hydroxide, at 25 °C for 2 minutes or less.
  • aqueous alkaline systems such as aqueous solutions containing 0.262 N tetramethylammonium hydroxide, at 25 °C for 2 minutes or less.
  • the photoresist layer will be removed during development in portions which are unexposed to UV radiation, but will be substantially unaffected in exposed portions.
  • Development of a negative-working resist typically consists of treatment with a critical fluid or an organic solvent.
  • a critical fluid as used herein, is a substance heated to a temperature near or above its critical temperature and compressed to a pressure near or above its critical pressure.
  • Critical fluids in this invention are at a temperature that is higher than 15 °C below the critical temperature of the fluid and are at a pressure higher than 5 atmospheres below the critical pressure of the fluid.
  • Carbon dioxide can be used for the critical fluid in the present invention.
  • Various organic solvents can also be used as developer in this invention. These include, but are not limited to, halogenated solvents and non-halogenated solvents. Halogenated solvents are preferred and fluorinated solvents are more preferred.
  • a critical fluid can comprise one or more chemical compounds. Substrate
  • the substrate employed in this invention can illustratively be silicon, silicon oxide, silicon oxynitride, silicon nitride, or various other materials used in semiconductive manufacture.
  • T transmittance as defined below.
  • Transmittance Transmittance, T, ratio of the radiant power transmitted by a sample to the radiant power incident on the sample and is measured for a specified wavelength ⁇
  • UV Ultraviolet region of the electromagnetic spectrum which ranges from 10 nanometers to 390 nanometers
  • the DSC unit used is a Model DSC2910 made by TA Instruments, Wilmington, DE.
  • Samples are first spin-coated on silicon wafers on a Brewer Cee (Rolla, MO), Spincoater/Hotplate model 100CB. a) Two to four silicon wafers are spun at different speeds
  • x 0.80" thick are selected and each is run as a reference data file on a McPherson Spectrometer (Chemsford, MA), 234/302 monochrometer, using a 632 Deuterium Source, 658 photomultiplier, and Keithley 485 picoammeter.
  • Two speeds are selected from the silicon wafer data a) to spin the sample material onto the CaF 2 reference substrates (e.g., 2000 and 4000 rpm) to achieve the desired film thickness. Then each is baked at 120 °C for 30 min.
  • sample spectra is collected on the McPherson Spectrometer; the sample files are then divided by the reference CaF files, d) The resulting absorbance files are then adjusted (sample film on CaF 2 divided by CaF blank) for film thickness to give absorbance per micron (abs/mic), which is done using
  • the term "clearing dose” indicates the minimum exposure energy density (e.g., in units of mJ/cm 2 ) to enable a given photoresist film, following exposure, to undergo development.
  • a solution of 9.6 g Perkadox®16N and 70 mL methyl acetate diluted to 100 mL with Solkane 365 mfc was pumped into the reactor at a rate of 2.0 mL/minute for 6 minutes, and then at a rate of 0.1 mL/minute for 8 hours. After 16 hours reaction time, the vessel was cooled to room temperature and vented to 1 atmosphere. The recovered polymer solution was added slowly to an excess of hexane while stirring. The precipitate was filtered, washed with hexane and air dried. The resulting solid was dissolved in a mixture of THF and Solkane 365 mfc and added slowly to excess hexane.
  • a solution of 7.3 g Perkadox®16N and 60 mL methyl acetate diluted to 100 mL with Solkane 365 mfc was pumped into the reactor at a rate of 2.0 mL/minute for 6 minutes, and then at a rate of 0.1 mL/minute for 8 hours.
  • the vessel was cooled to room temperature and vented to 1 atmosphere.
  • the recovered polymer solution was added slowly to an excess of hexane while stirring.
  • the precipitate was filtered, washed with hexane and air dried.
  • the resulting solid was dissolved in a mixture of THF and Solkane 365 mfc and added slowly to excess hexane.
  • EXAMPLE 4 Copolymer of TFE. NB-F-OH. MAdA and HAdA
  • the procedure of Example 2 was followed except that 80.4 g NB-F- OH, 4.22 g MAdA, 1.07 g HAdA and 25 mL Solkane® 365 were used and a TFE pressure of 280 psi was maintained during the polymerization.
  • a solution of 72.5 g of NB-F-OH, 29.33 g MAdA and 7.4 g HAdA diluted to 100 mL with Solkane 365 mfc was pumped into the reactor at a rate of 0.10 mL/minute for 12 hr.
  • a solution of 9.6 g Perkadox®16N and 60 mL methyl acetate diluted to 100 mL with Solkane® 365 mfc was pumped into the reactor at a rate of 2.0 mL/minute for 6 minutes, and then at a rate of 0.1 mL/minute for 8 hours. After 16 hours reaction time, the vessel was cooled to room temperature and vented to 1 atmosphere. The recovered polymer solution was added slowly to an excess of heptane while stirring. The precipitate was filtered, washed with heptane and air-dried.
  • a metal pressure vessel of approximate 270 mL capacity was charged with 76.56 g NB-F-OH, 4.75 g MAdA, 3.20 g HAdA, 7.2 g tetrahydrofuran chain transfer agent and 25 mL Solkane® 365.
  • the vessel was closed, cooled to about -15 °C and pressured to 400 psi with nitrogen and vented several times.
  • the 1 reactor contents were heated to 50 °C.
  • TFE was added to a pressure of 270 psi and a pressure regulator was set to maintain the pressure at 270 psi throughout the polymerization by adding TFE as required.
  • a solution of 36.54 g of NB-F-OH, 23.10 g MAdA and 15.32 g HAdA diluted to 100 mL with Solkane® 365 mfc was pumped into the reactor at a rate of 0.10 mL/minute for 12 hr.
  • a solution of 9.96 g Perkadox®16N and 60 mL methyl acetate diluted to 100 mL with Solkane® 365 mfc was pumped into the reactor at a rate of 2.0 mL/minute for 6 minutes, and then at a rate of 0.1 mL/minute for 8 hours. After 16 hours reaction time, the vessel was cooled to room temperature and vented to 1 atmosphere.
  • a solution of 36.54 g of NB-F-OH, 30.62 g MAdA and 7.73 g HAdA diluted to 100 mL with Solkane® 365 mfc was pumped into the reactor at a rate of 0.10 mL/minute for 12 hr.
  • a solution of 9.96 g Perkadox®16N and 60 mL methyl acetate diluted to 100 mL with Solkane® 365 mfc was pumped into the reactor at a rate of 2.0 mL/minute for 6 minutes, and then at a rate of 0.1 mL/minute for 8 hours. After 16 hours reaction time, the vessel was cooled to room temperature and vented to 1 atmosphere.
  • the wafer was prepared by applying a priming layer of hexamethyldisilazane (HMDS) using a YES-3 vapor prime oven (Yield Engineering Systems, San Jose, CA). The oven was programmed to give a 5 minute prime at 150-160 °C.
  • HMDS hexamethyldisilazane
  • YES-3 vapor prime oven Yield Engineering Systems, San Jose, CA.
  • the oven was programmed to give a 5 minute prime at 150-160 °C.
  • 2 mL of the above solution after filtering through a 0.45 ⁇ m PTFE syringe filter, was deposited on the primed wafer and spun at 2500 rpm for 60 seconds and then baked at 120 °C for 60 seconds.
  • 248 nm imaging was accomplished by exposing the coated wafer to light obtained by passing broadband UV light from an ORIEL Model-82421 Solar Simulator (1000 watt) through a 248 nm interference filter which passes about 30% of the energy at 248 nm. Exposure time was 100 seconds, providing an unattenuated dose of 134 mJ/cm 2 . By using a mask with 18 positions of varying neutral optical density, a wide variety of exposure doses were generated. After exposure the exposed wafer was baked at 120 °C for 60 seconds.
  • TMAH tetramethylammonium hydroxide
  • a coated wafer was prepared, imaged, and developed as in Example 7. This test generated a positive image with a clearing dose of approximately 14.6 mJ/cm 2 .
  • EXAMPLE 9 Imaging of Polymer of TFE/NB-F-OH/MAdA/HAdA A solution was prepared as in Example 7, except that the TFE/NB-F- OH/MAdA/HAdA polymer in Example 5 was used, and magnetically stirred overnight. A coated wafer was prepared, imaged, and developed as in Example 7. This test generated a positive image with a clearing dose of approximately 7.6 mJ/cm 2 .
  • Example 8 A solution was prepared as in Example 8, except that the TFE/NB-F- OH/MAdA/HAdA polymer in Example 5 was used, and magnetically stirred overnight. A coated wafer was prepared, imaged, and developed as in Example 7. This test generated a positive image with a clearing dose of approximately 7.6 mJ/cm 2 .
  • EXAMPLE 11 Imaging of Polymer of TFE/NB-F-OH/MAdA/HAdA A solution was prepared as in Example 7, except that the TFE/NB-F- OH/MAdA/HAdA polymer in Example 6 was used, and magnetically stirred overnight. A coated wafer was prepared, imaged, and developed as in Example 7. This test generated a positive image with a clearing dose of approximately 7.6 mJ/cm 2 .
  • Example 6 OH/MAdA/HAdA polymer in Example 6 was used, and magnetically stirred overnight. A coated wafer was prepared, imaged, and developed as in Example 7. This test generated a positive image with a clearing dose of approximately 7.6 mJ/cm 2 .

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymères fluorés utiles dans des compositions de résines photosensibles ainsi que des procédés associés de microlithographie. Ces polymères et résines photosensibles comportent un groupe fonctionnel alcool fluoré conférant simultanément la transparence au rayonnement ultraviolet lointain et le développement en milieu basique. Les polymères comportent aussi une unité de répétition dérivée d'un comonomère de C1-C25 alkylhydroxyméthacrylate, par exemple du tert-butylhydroxyméthacrylate, ou d'un C5-C50 alkylacrylate polycyclique dans lequel le groupe polycyclique contient un groupe hydroxy, par exemple de l'hydroxyadamantylacrylate. Les matériaux de l'invention sont transparents aux UV lointains, particulièrement aux longueurs d'ondes courtes, par exemple 193 et 157 nm, ce qui les rend très utiles concernant la lithographie à ces longueurs d'ondes.
PCT/US2003/022912 2002-07-26 2003-07-23 Polymeres fluores, resines photosensibles et procedes de microlithographie WO2004011509A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU2003254112A AU2003254112A1 (en) 2002-07-26 2003-07-23 Fluorinated polymers, photoresists and processes for microlithography
EP03771715A EP1551887A4 (fr) 2002-07-26 2003-07-23 Polymeres fluores, resines photosensibles et procedes de microlithographie
JP2004524696A JP4303202B2 (ja) 2002-07-26 2003-07-23 弗素化ポリマー、フォトレジストおよびミクロ平版印刷のための方法
US10/521,412 US20050203262A1 (en) 2002-07-26 2003-07-23 Fluorinated polymers, photoresists and processes for microlithography
CA002493926A CA2493926A1 (fr) 2002-07-26 2003-07-23 Polymeres fluores, resines photosensibles et procedes de microlithographie

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US39889902P 2002-07-26 2002-07-26
US60/398,899 2002-07-26

Publications (1)

Publication Number Publication Date
WO2004011509A1 true WO2004011509A1 (fr) 2004-02-05

Family

ID=31188514

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/022912 WO2004011509A1 (fr) 2002-07-26 2003-07-23 Polymeres fluores, resines photosensibles et procedes de microlithographie

Country Status (9)

Country Link
US (1) US20050203262A1 (fr)
EP (1) EP1551887A4 (fr)
JP (1) JP4303202B2 (fr)
KR (1) KR20050030639A (fr)
CN (1) CN1678646A (fr)
AU (1) AU2003254112A1 (fr)
CA (1) CA2493926A1 (fr)
TW (1) TW200403262A (fr)
WO (1) WO2004011509A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118656A2 (fr) * 2004-05-20 2005-12-15 E.I. Dupont De Nemours And Company Photoresines comprenant des polymeres derives de monomeres polycycliques substitues par un alcool fluore
CN1946751B (zh) * 2004-04-27 2010-12-08 东京应化工业株式会社 用于形成液浸曝光工艺用光刻胶保护膜的材料、以及使用该保护膜的光刻胶图案形成方法
CN102070755A (zh) * 2010-11-09 2011-05-25 浙江理工大学 一种三嵌段氟化聚合物及制备方法
US7960087B2 (en) * 2005-03-11 2011-06-14 Fujifilm Corporation Positive photosensitive composition and pattern-forming method using the same
WO2016091743A1 (fr) 2014-12-12 2016-06-16 Carl Zeiss Smart Optics Gmbh Dispositifs d'affichage

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4772288B2 (ja) * 2003-06-05 2011-09-14 東京応化工業株式会社 ホトレジスト組成物用樹脂、ホトレジスト組成物、およびレジストパターン形成方法
JP4188265B2 (ja) 2003-10-23 2008-11-26 東京応化工業株式会社 レジスト組成物およびレジストパターン形成方法
US8530148B2 (en) 2006-12-25 2013-09-10 Fujifilm Corporation Pattern forming method, resist composition for multiple development used in the pattern forming method, developer for negative development used in the pattern forming method, and rinsing solution for negative development used in the pattern forming method
JP4554665B2 (ja) 2006-12-25 2010-09-29 富士フイルム株式会社 パターン形成方法、該パターン形成方法に用いられる多重現像用ポジ型レジスト組成物、該パターン形成方法に用いられるネガ現像用現像液及び該パターン形成方法に用いられるネガ現像用リンス液
US8637229B2 (en) * 2006-12-25 2014-01-28 Fujifilm Corporation Pattern forming method, resist composition for multiple development used in the pattern forming method, developer for negative development used in the pattern forming method, and rinsing solution for negative development used in the pattern forming method
US8603733B2 (en) 2007-04-13 2013-12-10 Fujifilm Corporation Pattern forming method, and resist composition, developer and rinsing solution used in the pattern forming method
KR100990106B1 (ko) 2007-04-13 2010-10-29 후지필름 가부시키가이샤 패턴형성방법, 이 패턴형성방법에 사용되는 레지스트 조성물, 현상액 및 린스액
US8034547B2 (en) 2007-04-13 2011-10-11 Fujifilm Corporation Pattern forming method, resist composition to be used in the pattern forming method, negative developing solution to be used in the pattern forming method and rinsing solution for negative development to be used in the pattern forming method
WO2008140119A1 (fr) 2007-05-15 2008-11-20 Fujifilm Corporation Procédé de formation d'un motif
US8476001B2 (en) 2007-05-15 2013-07-02 Fujifilm Corporation Pattern forming method
JP4617337B2 (ja) 2007-06-12 2011-01-26 富士フイルム株式会社 パターン形成方法
US8617794B2 (en) 2007-06-12 2013-12-31 Fujifilm Corporation Method of forming patterns
US8632942B2 (en) 2007-06-12 2014-01-21 Fujifilm Corporation Method of forming patterns
JP4590431B2 (ja) 2007-06-12 2010-12-01 富士フイルム株式会社 パターン形成方法
KR101705670B1 (ko) 2007-06-12 2017-02-10 후지필름 가부시키가이샤 네가티브 톤 현상용 레지스트 조성물 및 이것을 사용한 패턴형성방법
KR101768929B1 (ko) * 2010-09-30 2017-08-17 디아이씨 가부시끼가이샤 함불소 중합성 수지, 그것을 사용한 활성 에너지선 경화형 조성물 및 그 경화물
JP6148112B2 (ja) * 2013-04-02 2017-06-14 リソテック ジャパン株式会社 光透過度測定方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080524A (en) * 1998-06-02 2000-06-27 Samsung Electronics Co., Ltd. Photosensitive polymer having cyclic backbone and resist composition comprising the same
US20020119398A1 (en) * 2000-10-12 2002-08-29 Desimone Joseph M. CO2-processes photoresists, polymers, and photoactive compounds for microlithography
US20030215735A1 (en) * 2000-05-05 2003-11-20 Wheland Robert Clayton Copolymers for photoresists and processes therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444148A (en) * 1964-10-05 1969-05-13 Du Pont Copolymers of selected polyfluoroper-haloketone adducts with other selected ethylenic compounds
EP1183571B1 (fr) * 1999-05-04 2010-06-02 E.I. Du Pont De Nemours And Company Photoresines fluorees et procedes de microlithographie
US20030022097A1 (en) * 2000-05-05 2003-01-30 Arch Specialty Chemicals, Inc Tertiary-butyl acrylate polymers and their use in photoresist compositions
US6838225B2 (en) * 2001-01-18 2005-01-04 Jsr Corporation Radiation-sensitive resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080524A (en) * 1998-06-02 2000-06-27 Samsung Electronics Co., Ltd. Photosensitive polymer having cyclic backbone and resist composition comprising the same
US20030215735A1 (en) * 2000-05-05 2003-11-20 Wheland Robert Clayton Copolymers for photoresists and processes therefor
US20020119398A1 (en) * 2000-10-12 2002-08-29 Desimone Joseph M. CO2-processes photoresists, polymers, and photoactive compounds for microlithography

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1946751B (zh) * 2004-04-27 2010-12-08 东京应化工业株式会社 用于形成液浸曝光工艺用光刻胶保护膜的材料、以及使用该保护膜的光刻胶图案形成方法
WO2005118656A2 (fr) * 2004-05-20 2005-12-15 E.I. Dupont De Nemours And Company Photoresines comprenant des polymeres derives de monomeres polycycliques substitues par un alcool fluore
WO2005118656A3 (fr) * 2004-05-20 2006-01-12 Du Pont Photoresines comprenant des polymeres derives de monomeres polycycliques substitues par un alcool fluore
US7960087B2 (en) * 2005-03-11 2011-06-14 Fujifilm Corporation Positive photosensitive composition and pattern-forming method using the same
CN102070755A (zh) * 2010-11-09 2011-05-25 浙江理工大学 一种三嵌段氟化聚合物及制备方法
CN102070755B (zh) * 2010-11-09 2013-01-09 浙江理工大学 一种三嵌段氟化聚合物及制备方法
WO2016091743A1 (fr) 2014-12-12 2016-06-16 Carl Zeiss Smart Optics Gmbh Dispositifs d'affichage

Also Published As

Publication number Publication date
JP4303202B2 (ja) 2009-07-29
AU2003254112A1 (en) 2004-02-16
CN1678646A (zh) 2005-10-05
EP1551887A4 (fr) 2008-07-02
TW200403262A (en) 2004-03-01
CA2493926A1 (fr) 2004-02-05
KR20050030639A (ko) 2005-03-30
JP2005533907A (ja) 2005-11-10
EP1551887A1 (fr) 2005-07-13
US20050203262A1 (en) 2005-09-15

Similar Documents

Publication Publication Date Title
US6790587B1 (en) Fluorinated polymers, photoresists and processes for microlithography
US7276323B2 (en) Photoresists, polymers and processes for microlithography
US6872503B2 (en) Copolymers for photoresists and processes therefor
JP4402304B2 (ja) フッ素化ポリマー、フォトレジストおよびミクロリソグラフィーのための方法
US20050203262A1 (en) Fluorinated polymers, photoresists and processes for microlithography
US20040023150A1 (en) Photoresists, polymers and processes for microlithography
EP1240554A2 (fr) Photoresists a base de nitrile/fluoroalcool et procedes de microlithographie associes
US6884564B2 (en) Fluorinated polymers having ester groups and photoresists for microlithography
EP1379920A2 (fr) Bases et tensioactifs, et leur utilisation dans des compositions de photor sine pour microlithogravure
EP1383812B1 (fr) Fluoropolymeres polycycliques et photoresines pour microlithogravure
KR101017801B1 (ko) 히드록실화된 광산-분해가능한 기를 갖는 포토레지스트
US7019092B2 (en) Fluorinated copolymers for microlithography
US7312287B2 (en) Fluorinated polymers useful as photoresists, and processes for microlithography
US20040092686A1 (en) Polycyclic fluorine-containing polymers and photoresists for microlithography
WO2004022612A1 (fr) Resines photosensibles, fluoropolymeres et procedes des microlithographie a 157 nm

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003771715

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2003817569X

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2493926

Country of ref document: CA

Ref document number: 2004524696

Country of ref document: JP

Ref document number: 1020057001370

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020057001370

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 10521412

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2003771715

Country of ref document: EP